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  • 101
    Electronic Resource
    Electronic Resource
    Determination of osmotic coefficients in polyelectrolyte solutions by potentionmetric measurements during phase separation (1967)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 1055-1059 
    Details
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A method of evaluating osmotic coefficients of polyelectrolyte solutions is suggested for systems in which a two-phase equilibrium is maintained between the polymer solution and a polymer precipitate so that the “polymer” terms Cpdμp in the Gibbs-Duhem relationship may be neglected. The method is applied to a polybase system, and the osmotic coefficients calculated from the experimental data are discussed in terms of the theory of Alexandrowicz. The results are found to be in line with the above theory but the characteristic parameter φp, the fraction of free counterions, is about twice as large as values previously observed in polyacids.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1967.160050605
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  • 102
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    Comparison of osmotic pressures from EMF measurements, obtained according to cell-model considerations and exact Gibbs-Duhem integrations (1967)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 1061-1066 
    Details
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Osmotic pressures of aqueous solutions of poly(diethylaminoethyl methacrylate) hydrochloride, in equilibrium with a precipitate of the un-ionized polybase, at various concentrations of polymer and NaCl in solution and at different values of pH are derived from emf measurements and the “cell” theory for polyelectrolytes. Single-ion activities are evaluated according to two procedures. The first is based on measurements with ion-specific electrodes versus a calomel electrode. The second makes use of a salt bridge, but assumes that the co-ions have activity coefficients equal to the mean activity coefficient of the salt in a polyelectrolyte-free solution of the same concentration. The results show that the calculated values of the osmotic pressures are consistent with those obtained by the exact integration of the Gibbs-Duhem relationship, when the first procedure is employed. If, however, the single-ion activities are evaluated by the second procedure, the osmotic pressures obtained are consistently lower by about 10%. These differences arise because the two methods yield different values of the activity coefficients of the single ions.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1967.160050606
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  • 103
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    Time-temperature superposition of the dynamic birefringence of polyethylene (1967)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 1079-1086 
    Details
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The dynamic strain-optical coefficient of low-density polyethylene is found to decrease with increasing frequency and increase with increasing temperature (at temperatures up to 60°C.). It is found that a series of curves representing the real, K′, and imaginary, K″, parts of the frequency variation of the strain-optical coefficient obtained at various temperatures up to 60°C. may be superposed by translation along the frequency axis. The temperature dependence of the shift factor corresponds to an Arrhenius type equation with an activation energy of the order of 25 kcal./mole. This may be compared with the similar value obtained by Takayanagi for the αc′ mechanical loss and with the dynamic x-ray diffraction values reported by Kawaguchi et al., but is somewhat lower than the value of 34 kcal./mole reported by Onogi et al. from birefringence relaxation studies. Takayanagi has ascribed the αc′ peak to cooperative motion of crystalline and amorphous regions of the sort that might be involved in the suggested sliding of lamellae over each other. At temperatures higher than 80°C., horizontal superposition is not possible.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1967.160050608
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  • 104
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    Time-temperature superposition of time-dependent birefringence for low-density polyethylenePaper presented at the International Symposium on Macromolecular Chemistry, Tokyo and Kyoto, Japan, October 3, 1966. (1967)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 1067-1078 
    Details
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The time-dependent birefringence has been measured simultaneously with the stress relaxation on quenched and annealed low-density polyethylene at various temperatures from 10 to 70°C. The strain-optical coefficient increases generally with increasing time, and approaches the equilibrium value, which depends upon the temperature. When the strain-optical coefficient at a fixed time is plotted against temperature, it first increases and then decreases after passing through a maximum at Tmax with increasing temperature. The higher the degree of crystallinity, the higher are the equilibrium values of the strain-optical coefficient and Tmax. The curves for strain-optical coefficient versus time and relaxation modulus versus time below Tmax can be superposed well by a horizontal shift along the abscissa. The optical shift factor obeys the original WLF equation, while the mechanical shift factor is much larger than the optical one. The molecular mechanisms corresponding to this dispersion of the strain-optical coefficient and viscoelastic αc absorption peak near Tmax are discussed.
    Additional Material: 12 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1967.160050607
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  • 105
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    NMR spectra of poly-2-vinylpyridine (1967)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 1320-1322 
    Details
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1967.160050630
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  • 106
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    On polymorphism in polypentene-1 (1967)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 1323-1325 
    Details
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1967.160050631
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  • 107
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    Light scattering study of the molecular weight distribution of polypropylene (1967)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 1329-1329 
    Details
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1967.160050633
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  • 108
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    Some studies of the crystallization of polychlorotrifluoroethylene copolymer films (1968)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 31-61 
    Details
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A fluorocarbon copolymer of chlorotrifluoroethylene (96%) and vinylidene fluoride has been isothermally crystallized and the quenched films analyzed by the light microscope, photographic light-scattering, and density measurements. Above a supercooling of 79°C., homogeneous nucleation dominates, giving a morphology that appears to be that of a twisted ribbon. At supercoolings below 79°C., heterogeneous nucleation dominates and leads to spherulitic morphology. Sheaf or rodlike morphology occurs at very low supercoolings. Crystallization rates determined from density measurements at room temperature indicate maximum rate due to heterogeneous nucleation occurring at a supercooling greater than 79°C., but the temperature for maximum rate cannot be identified because of the transition to homogeneous nucleation which causes a discontinuity in the rate versus temperature curve. Superposability of crystallization isotherms constructed from density values are inconsistent with the large melting point lowering from that of polychlorotrifluoroethylene for this copolymer. However, this may be explained by the presence of a different crystal system for each monomer in the copolymer.
    Additional Material: 25 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1968.160060102
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  • 109
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    Temperature dependence of the growth rate of spherulites (1968)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 165-180 
    Details
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The spherulitic growth data that exist in the literature for a wide diversity of polymers have been analyzed according to various possible nucleation mechanisms. It is demonstrated that, if allowed a reasonable choice for the equilibrium melting temperature, no unbiased selection of a unique nucleation process can be made. Moreover, a set of universal parameters exists for each of the allowable nucleation processes which enables the data to be represented by a single straight line which encompasses all the polymers. The only quantities specific to a given polymer are the equilibrium melting temperature and the activation energy for transport. The magnitude of the latter quantity is shown to be dependent on the glass temperature of the polymer.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1968.160060109
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  • 110
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    Transition temperatures and crystallinity in polyoctadecene-1 (1968)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 241-248 
    Details
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polyoctadecene-1, as isolated from a Ziegler-type polymerization, was examined by density and refractive index measurements and by differential thermal analysis. Two main transitions were observed, their sharpness suggesting that they are both first-order. Extraction with n-hexane at 25°C. separated the polymer into two almost equal fractions, each showing essentially one of these transitions. Transition temperatures were compared with those of certain other polymers having long n-alkyl side chains. From this comparison, and from the findings of other workers, it was concluded that the polymer of lower transition temperature is atactic polyoctadecene, in which the side chains only participate in crystallization, whereas the polymer of higher transition temperature is tactic polyoctadecene, in which crystallization involves both the main chain and side chains.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1968.160060114
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  • 111
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    Kinetic interpretation of the glass transition: Glass temperatures of n-alkane liquids and polyethylene (1968)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 249-257 
    Details
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: On the basis of an isoviscosity criterion for the glass transition (ηg ⋍ 1013 poise) in liquids of low molecular weight, theoretical Tg values were calculated for the n-alkane series by the equation log η = log A + B/(T - T0), with the use of values reported by Lewis for the parameters. The Tg/T0 ratio reaches a limiting value of 1.25 and φg = (Tg - T0)/2.3B = 0.027, a constant. Extrapolation to (CH2)∞ gives Tg = 200°K., T0 = 160°K., and B = 640°K. This Tg is consistent with other estimates for poly-ethylene, and T0 coincides with the temperature at which the “excess” liquid entropy for (CH2)∞ becomes zero from thermodynamic data. For polymer liquids it is proposed that E0 = 2.3RB is determined by the internal barriers to rotation for the “isolated” polymer chains. Thus, E0 = 2.9 kcal./mole for polyethylene, 3.0 kcal./mole for polystyrene, 5.7 kcal./mole for polyisobutylene, and 1.9 kcal./mole for polydimethylsiloxane.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1968.160060115
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  • 112
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    Change with temperature of the ESR spectra of peroxy radicals trapped in irradiated polytetrafluoroethylenePaper presented at the 18th Chemical Society Meeting, Kyoto, Japan, April 5, 1965. (1968)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 265-279 
    Details
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The ESR spectra of peroxy radicals in irradiated powders and oriented samples of polytetrafluoroethylene (PTEE) have been measured with a K-band spectrometer, and the principal values and directions of the g tensor were determined both at room temperature and at 77°K. In contrast to the spectra of the usual peroxy radicals, those trapped in γ-irradiated PTFE exhibited an ESR spectrum apparently having a larger principal value for g⊥ than for g∥ when measured at room temperature, although the normal principal values were observed at 77°K. As for the directions of the principal axes, g∥ was directed along the chain axis at room temperature and was perpendicular to the chain axis at 77°K. From the temperature change of the g tensor and the line shapes in the oriented samples, it is shown that the observed temperature change of the spectra is due to rapid rotation at room temperature around the chain axis rather than around the C—O bond axis. Assuming this, the apparent principal values of the g tensor at room temperature were calculated from the g tensor obtained at 77°K. for the rigid state, and the results are in good agreement with observations at room temperature. A structure for the peroxy radicals is also proposed. In addition, the spectral line shape function for the uniaxially oriented samples has been derived.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1968.160060117
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  • 113
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    Anomalous plugging of sintered glass filters by high molecular weight polymers (1968)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 294-299 
    Details
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1968.160060120
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  • 114
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    Liquid-liquid phase separation in multicomponent polymer solutions. II. The critical state (1968)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 325-347 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Theoretical and experimental evidence is put forward to prove that the determination of the phase-volume ratio as a function of temperature and concentration is a sensitive and simple means of determining the liquid-liquid critical state. Knowledge of the critical conditions permits very accurate calculations of the interaction parameter g in the free-energy function. In experiments with polystyrene-cyclohexane, g was found to depend on the concentration. The value of g and its concentration dependence agree very well with the results of osmotic measurements by Rehage and Palmen. In experiments with polyethylene-diphenyl ether, g proved to be independent of concentration in the range of measurement. The temperature function was found to be: g = -0.6086 + 482.2/T (at 137-148°C.). Gibbs' expressions for the critical conditions were worked out for a free-energy relation in the form of an extended Flory-Huggins function.
    Additional Material: 11 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1968.160060202
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  • 115
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    Liquid-liquid phase separation in multicomponent polymer solutions. III. Cloud-point curves (1968)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 349-366 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Cloud-point curves (CPC) were calculated on the basis of the Flory-Huggins free-energy relation for various hypothetical polymer samples dissolved in a single solvent. Molecular weight distributions varying widely in shape and width were examined. The shape of the CPC reflects details of the molecular weight distribution. This appears from the location of the critical point on the right-hand branch of the CPC. The latter often shows a depression, which becomes more distinct as the Mz/Mw value increases. These theoretical results were confirmed experimentally with the system polyethylene-diphenyl ether. With the aid of the theoretical data collected it was possible to explain the remarkable agreement between the θ temperatures determined by light-scattering and by the Shultz-Flory method. The latter method is basically incorrect, since it identifies the polymer solution with a binary mixture. An explanation could also be given for the empirical relation which McIntyre et al. recently found between the shape of the top of the CPC and the width of the molecular weight distribution.
    Additional Material: 12 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1968.160060203
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  • 116
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    Electric properties of macromolecules. XIII. Transient electric birefringence of sodium polyethylenesulfonate solutions (1968)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 421-431 
    Details
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The electric birefringence of sodium polyethylenesulfonate in water has been studied. For a low molecular weight fraction, the electric field dependence followed the Kerr law quite closely. For a higher molecular weight fraction, the specific Kerr constant was much larger, and pronounced saturation of the electric birefringence was observed in fields of 15 kv./cm. The specific Kerr constant increased with decreasing polyelectrolyte concentration in pure water. On the other hand, it decreased on isoionic dilution. The saturation effect was the more marked, the lower the polyelectrolyte concentration. The saturation behavior resembled that of permanent dipole orientation, but this mechanism was not supported by the build-up of the birefringence. The magnitudes of specific Kerr constants of various types of macromolecules in solution are tabulated and discussed.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1968.160060207
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  • 117
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    Secondary processes of poly(methyl methacrylate) and their activation energies as determined by shear and tensile creep compliance measurementsPresented in part at the 37th Meeting of the Society of Rheology, Atlantic City, New Jersey, October 31-November 2, 1966. (1968)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 433-449 
    Details
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The results of measurement of the shear and tensile creep compliance of poly(methyl methacrylate) between -150 and 75°C. are presented. The master curves show the creep behavior from essentially elastic response to the onset of the α-process. The logarithmic retardation spectra and shear loss compliance reveal two molecular processes, one process being partially obscured by the α-process and therefore not as well defined as the other. These processes manifest themselves as breaks in an Arrhenius plot of the shift factors at about -35 and +25°C. The activation energies in the -35 to 25°C. and 25 to 80°C. ranges are 17.8 kcal./mole and 42.2 kcal./mole, respectively. The former temperature range and activation energy corresponds to the well-known ß-process in poly(methyl methacrylate), the latter to a process which is apparently detectable using various long-time experimental techniques but whose molecular interpretation is at present obscure. The activation energy in the -150 to -35°C. range is about 8.7 kcal./mole.
    Additional Material: 9 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1968.160060301
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  • 118
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    Nuclear magnetic resonance of poly-β-alanine (1968)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 493-498 
    Details
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Nuclear magnetic resonance of poly-β-alanine samples differing in solubility in water was studied over a wide temperature range as part of an investigation of their physical properties. Water-soluble poly-β-alanine has more branches and a lower degree of crystallinity than water-insoluble poly-β-alanine. NMR spectra of poly-β-alanine show one component at 77°K. which splits into two components, broad and narrow, at room temperature. Two transition regions were observed in curves for line width and second moment versus temperature. The higher transition temperature, corresponding to the glass transition of the polymer, appears to decrease with increasing water content. The second moment for the water-soluble polymer differs from that of the water-insoluble polymer at 77°K. This is interpreted in terms of the difference in the degree of crystallinity of the polymers.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1968.160060306
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  • 119
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    Viscoelastic properties of polybutadienes - linear and lightly crosslinked near the gel point (1968)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 479-492 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Viscoelastic properties of four linear and three very lightly crosslinked polybutadienes (microstructure about 50% trans) were studied. Of the latter, two had not reached the gel point, and their molecular weight distributions were determined by sedimentation velocity analysis; the third was crosslinked just past the gel point, with only 32% gel fraction present. The crosslinking agent was sulfur. Complex shear compliances were measured over a frequency range from 0.1 to 1000 cps at temperatures from -70 to 30°C. with a Fitzgerald transducer and a Plazek torsion pendulum; and torsional creep measurements were made over time periods up to about three days. The creep data were converted to the corresponding dynamic viscoelastic functions at very low frequencies by conventional approximation methods. All data were reduced to 25°C. by shift factors calculated from a previously adopted equation of the WLF form. In the transition zone, the viscoelastic properties of linear samples were almost independent of molecular weight. The entanglement spacing, derived from the minimum in the loss tangent and the inflection in the storage compliance, was 130 to 160 chain atoms. The maximum in the retardation spectrum attributable to motions of individual network strands was closely similar to the corresponding maxima for more highly crosslinked vulcanizates previously studied, showing that even in the latter it is associated with entanglement network strands rather than strands between chemical crosslinks. For a linear sample with molecular weight 180,000, the retardation processes disappear at times beyond about 10 sec. at 25°C. With crosslinking short of the gel point (i.e., branching) the slow retardation processes are enormously increased and prolonged to longer times. With further crosslinking through the gel point and beyond, the slow retardation processes decrease progressively in magnitude. Qualitatively, this behavior resembles the sharp maximum in content of highly branched and aggregated molecular species which is predicted at the gel point by crosslinking statistics; but the slow processes (or low-frequency losses) persist farther past the gel point than would be expected on this basis. The steady-state compliances of the linear samples were smaller, but for a sample crosslinked short of the gel point were much larger, than the prediction of the Rouse theory modified for molecular weight distribution.
    Additional Material: 5 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1968.160060305
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    Variation of polymer chain dimensions with temperature below the theta point (1968)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 575-585 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The temperature dependence of the intrinsic viscosity [η] for the system polystyrene-cyclohexane in the interval -20 〈 (T - ψ) ≤ 0 near the ideal temperature ψ has been investigated. The observed diminution in size of the molecular coil with decreasing temperature is attributable to attractive net polymer-solvent interactions, denoted by negative values for the excluded volume parameter z. The data thus comprise an interesting selection for comparison with the predictions of various excluded volume theories. Among the approximate, closed-form expressions the functional relationship of Flory (x5 - α3 ∼ z) appears to describe best the variation of [η] with temperature in the region examined. The behavior of the Huggins constant k′ derived from the intrinsic viscosity plots is also examined, in accordance with the Peterson-Fixman model, suitably extended to the temperature region below ψ.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1968.160060312
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    Structure of a novel polyimide (1968)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 559-574 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The product of the thermal polymerization of ß-carboxymethyl caprolactam has been identified as a poly[(2,6-dioxo-1,4-piperidinediyl)trimethylene]. An indication of various chain conformations has been explained by the possible existence of two different conformations of the dioxopiperidine moiety. One conformation pertains to an equatorial position of the trimethylene moiety with respect to the plane of the imide group. The other is derived from a structural unit in which the trimethylene group is positioned axially to the plane of the ring. While the former conformation has been ascribed to the crystalline modification the latter appears to be the predominant structure of the polymer in formic acid solution as indicated by NMR analysis. In the glassy state the macromolecule is assumed to be composed of segments of either conformation. The unoriented linear polymer crystallizes upon annealing in positively birefringent spherulites. A triclinic unit cell with the following parameters: a = 9.64 A., b = 11.32 A., c = 15.80 A., α = 98°, β = 96°, γ = 114° has been found to contain eight structural units. The calculated density, 1.30 g./cm.3, agrees with experimental data. A crystal structure is proposed on the basis of the x-ray data.
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    Fuming nitric acid treatment of polyethylene. IV. Morphology of drawn polyethylene (1968)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 587-605 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Drawn PE of different draw ratios (ranging from 1 to 25) and thermal treatment (annealing temperature 80, 100, 110, 120, 127°C.) was treated with fuming nitric acid at 80°C. Weight loss, molecular weight, elastic modulus, and thermograms were measured for annealed and unannealed samples as a function of the treatment time and draw ratio. As a consequence of the preferential oxidation of the noncrystalline portions, there occurs initially a high rate of weight loss and a steep drop in molecular weight, followed by a lower rate of weight loss at nearly constant molecular weight. The elastic modulus stays practically constant up to the moment where the brittleness of the sample prevents further measurement. During the later period the thermograms exhibit one melting peak during the first melting. The remelt of the same sample, however, has two melting peaks with a relative intensity independent of the treatment time. That the two melting peaks are caused by two components of different molecular weights present in the sample is substantiated by fractionation. At very high annealing temperature (127°C.), two peaks appear, not only in the first melting curve of the etched sample, but also in the melting curve of the unetched material. Such an effect is the consequence of partial melting during annealing followed by new crystallization during cooling the sample to room temperature. The findings are related to the morphology of the drawn material under the assumption of preferential scission of chain loops in the amorphous-crystalline sandwich layer model.
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    Nuclear magnetic resonance study of drawn poly(ethylene glycol) (1968)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 653-656 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1968.160060317
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    Isochronal temperature-concentration diagram for a polymer-diluent system (1968)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 687-694 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: The results of an investigation of the viscoelastic and thermal properties of the gelatin-glycerol system are presented in the form of a complete temperature-composition diagram. This diagram shows the isochronal (10-sec.) mechanical behavior of the system along lines of constant modulus and thereby affords a convenient assessment of variation in viscoelastic behavior along any isotherm or isopleth of interest. Comparison of the results with previously obtained limited sets of data on a number of other polymer-dilent systems indicates the applicability and utility of such a presentation.
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    Ductile behavior of single crystal mats of an ethylene-propylene copolymer (1968)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 707-712 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: It is reported that mats formed by the sedimentation of single crystals of methyl- and ethyl-branched polyethylene exhibit strength and ductility comparable with that of melt-crystallized films. In fact, in the case of methyl-branched polymers, extensions of up to 50× were obtained on cold drawing. Observations on separate crystals suggest that this extension is due to the pulling out of individual lamellae. In view of the magnitude of the extension, this implies unfolding of the molecules. That considerable coherence can be obtained without original molecular ties between crystals is of significance as regards the molecular interpretation of the strength and ductility of crystalline polymers.
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    Unperturbed chain dimensions of isotactic polypropylene in theta solvents (1968)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 735-744 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: The unperturbed mean-square end-to-end distance 〈R02〉 and its temperature variation d In 〈R02〉/dT for isotactic polypropylene have been estimated from intrinsic viscosity data in three theta solvents, i.e., diphenyl, diphenyl ether, and dibenzyl ether, measured at their θ temperatures as determined by precipitation temperature measurements. The characteristic ratios, 〈R02〉/nl2, where n is the number of bonds of length l in the main chain, evaluated by assuming Φ = 2.87 × 1021, are 5.80 in diphenyl (at θ = 125.1°C.), 5.41 in diphenyl ether (at θ = 142.8°C.), and 4.56 in dibenzyl ether (at θ = 183.2°C.). These values lead to the temperature coefficient d In 〈R02〉/dT = -4.09 × 10-3 deg.-1 Results are compared with the data previously reported on polyethylene.
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    Acetylation of cellulose I and II studied by limiting viscosity and X-ray diffractionPaper presented in part at 153rd meeting of the American Chemical Society in Miami, Florida, April, 1967. (1968)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 745-773 
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    Keywords: Physics ; Polymer and Materials Science
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    Notes: When cellulose triacetates and some hydrolyzed acetates are boiled in 2.5N hydrochloric acid there is no residue. Under the same conditions cellulose is hydrolyzed, and a residue is obtained with a limiting viscosity that is related to the average length of the cellulose crystallites. These findings are combined to develop a method for studying the progress of acetylation through the amorphous portion of cellulose and into the crystallites, and to investigate the relative reactivities of cellulose I and cellulose II. Acetates were made from cotton and wood cellulose by a “fibrous” (heterogeneous) esterification involving sulfoacetic acid or perchloric acid catalyst in acetic acid-acetic anhydride; the final acetyl contents (10-41%) were attained by stopping the reaction at various points short of the triester (rather than by hydrolyzing a triester). When these acetates were boiled in 2.5N HCI they did not disappear completely, and the residues were cellulose I, indicating that cellulose acetate had been removed. With increasing acetyl the yield of residue decreased, and beyond about 33% acetyl the viscosity and x-ray measurements showed that the length and width of the crystallites decreased. However, when a nonsolvent such as toluene was added to the acetylation medium, the limiting viscosity did not change over the same acetyl range (up to 40%). Samples of varying acetyl values were taken during a regular acetylation of cotton linters in a mixer with sulfuric acid catalyst. X-ray studies of the residues obtained by boiling the acetates in 2.5N HCI revealed the presence of unreacted cellulose I even after 40% acetyl had been reached. This explains why the manufacture of cellulose esters from cellulose I requires complete esterification before they are hydrolyzed to the desired acetyl level. It was shown that there is a distinct difference between the acetylation reactivity of cellulose I and cellulose II. This indicates the importance of avoiding cellulose II formation during the refinement of cellulose for the manufacture of cellulose acetate in a process involving activation with acetic acid.
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    Phase equilibria in polymer-liquid-liquid systems (1968)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 813-823 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The phase equilibria in polymer-liquid 1-liquid 2 ternary systems have been calculated on the basis of the Flory-Huggins theory of polymer solutions. A new approximation method based on the “cluster” concept has been introduced for mixed solvents comprising a solvent and a nonsolvent. This concept has been verified with polystyrene-solvent-methanol systems.
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    Melting of polycaprolactam (1968)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 833-848 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: Highly crystalline polycaprolactam was prepared by zone polymerization of ε-caprolactam. Folded-chain crystallized and annealed, melt-crystallized, and solution-crystallized polycaprolactam was produced from commercial polycaprolactam. All samples were characterized by x-ray diffraction, electron microscopy, density measurement, and heat of fusion measurement. The determination of the time-dependent melting by DTA and scanning calorimetry revealed that all the different morphologies show different melting behavior. Zone-polymerized polycaprolactam superheats, and the other morphologies reorganize on heating to different degrees. Densities and heat of fusion vary in the same manner - from highest to lowest - in the order: zone-polymerized, solution-crystallized, annealed, and melt-crystallized. An estimate of heat of fusion, equilibrium melting point, and surface free energy was obtained from the melting points.
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    Heat capacities for atactic polystyrene of narrow molecular weight distribution to 360°K. (1968)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 849-860 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: Precise heat capacity values are reported over the temperature range from 10 to 360°K. for a sample of atactic polystyrene having a narrow molecular weight distribution. This sample was taken from the stock from which National Bureau of Standards Standard Sample 705, Narrow Molecular Weight Distribution Polystyrene, was established. Data are reported for the sample as received, and after an annealing procedure. At temperatures below about 60°K. a systematic difference comparable with the limits of experimental precision appears between the values obtained for the present sample as received and after the annealing, although at higher temperatures the values for the two conditions showed no systematic difference beyond the limits of precision of the measurements. At temperatures above 100°K., previously published values for atactic polystyrene samples of various molecular weight distributions and for isotactic polystyrene agree within about 0.5% of the values from this investigation. At temperatures below 100°K. significant heat capacity differences appear, especially between values for the atactic and the isotactic isomers, and even between atactic samples of different molecular weight distribution.
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    Conformations of Macromolecules (High Polymers, Vol. XXII), T. M. Birshtein and O. B. Ptitsyn. Trarislated from the Russian Edition by S. N. Timasheff and M. J. Timasheff. Interscience, New York, 1966, xiv + 350 pp. $14.50. (1968)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 1207-1208 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    URL: http://dx.doi.org/10.1002/pol.1968.160060613
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    Ionic bonding in butadiene copolymers. I. Network formation (1968)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 921-932 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: The mechanical effects of association between pendant ionic groups are investigated in series of butadiene-lithium methacrylate copolymers, butadiene-methyl (2-methyl-5-vinyl)-pyridinium iodide copolymers, and mixtures of these polyelectrolytes. Thermal and mechanical tests reveal a new transition above Tg in the pyridinium copolymers, designated Tt*. Below this temperature the materials behave like covalently crosslinked elastomers. The complex between the metal carboxylates appears thermally dissociable at all temperatures. The mixing of the oppositely charged polyelectrolytes leads to the formation of more stable intermolecular pyridinium carboxylate links.
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    Vibrational analysis of chain folding in polyethylene crystals (1968)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 995-1010 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The vibration frequencies of a polyethylene crystal lattice have been computed for various structures in which a fully deuterated chain is mixed with a normal chain. Intermolecular potential functions previously developed by the authors were used in the calculation. It is shown that such structures make it possible to distinguish experimentally between chain folding in the (110) plane and folding parallel to the (100) plane. Calculations have also been done for a regular polymer of (CH2CD2). Such a structure would permit the determination of the parity of the number of methylene groups in the fold.
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    Upturn effect in the Non-Newtonian intrinsic viscosity of polymer solutions. II. Polyisobutylene in polybutene oil (1968)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 1011-1020 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
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    Notes: With an increasing gradient, the intrinsic viscosity of a high molecular weight polyisobutylene (M̄n = 7 × 106) in polybutene oil L.100 (ηs = 5 poise) first drops to a minimum and then rises again. The minimum occurs at β = M[η]0ηsG/NkT = 240, which is about ten times the value predicted by the dumbbell model. Such a shift to larger gradient is in good agreement with the more realistic necklace model of macromolecules in a good solvent. The increase of intrinsic viscosity after the minimum is nearly linear with the gradient and continues beyond the value at zero gradient. Experiments with capillaries of different length-to-diameter ratios yield identical flow curves so that one may exclude the possibility that the observed upturn is an artifact caused by end effects or time dependence of viscosity.
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    Depolymerization studies on polyacetaldehyde (1968)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 1021-1033 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Depolymerization of amorphous polyacetaldehyde has been studied by measurements of weight loss versus time for thin films of the polymer in vacuum. Temperatures ranged from 40 to 80°C. The samples were prepared by freezing or melting the monomer in contact with treated glass surfaces. Light scattering, osmometry, and intrinsic viscosity measurements were used to characterize the polymers. Depolymerization rates were between second and third order with respect to the unvolatilized fraction, and the activation energy was 26.3 kcal. Much of the evidence points toward a slow unzipping reaction at the chain ends, but the analysis seems to be complicated by structural variations among the samples.
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    Phase relationships and thermodynamic interactions in isotactic polypropylene-diluent systems (1968)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 723-733 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: Phase relationships of isotactic polypropylene in various organic diluents were investigated. The diluents used were aliphatic alcohols, alkyl phenols, aryl phenols, diphenyl derivatives, alkyl aryl ethers, esters, and others. Among the diluents examined, n-butyl alcohol, p-tert-butyl phenol, p-tert-amyl phenol, diphenyl, diphenyl ether, benzyl phenyl ether, dibenzyl ether, and benzyl propionate were found to be theta solvents for isotactic polypropylene at temperatures in the range 120-190°C. For these theta solvents, the thermodynamic interaction parameters were determined. The results are discussed in relation to the type of diluent.
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    Nucleation of crystallization in molten isotactic polybutene-1 (1968)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 775-782 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
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    Notes: Droplet experiments have been performed on polybutene-1. It was found that this polymer can be cooled to room temperature without homogeneous nucleation of crystallization. It was also found that when the polymer was heterogeneously nucleated, form I (as well as form II) could be crystallized directly from the melt. The melting point of droplets crystallized in form I near room temperature decreased with increasing crystallization temperature, while the melting point of the droplets crystallized in form I at the highest temperatures increased with increasing crystallization temperature. There was a broad minimum at about 60°C. in the melting point versus crystallization temperature curve.
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    Viscoelasticity of oriented poly(ethylene terephthalate) (1968)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 787-793 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
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    Notes: Time-temperature superposition can be successfully applied to both the stress relaxation and dynamic mechanical properties of oriented PET fibers. Two curves result; one is the time dependence of the modulus at constant temperature, while the other is the shift, log aT, of this curve along the time scale as a function of temperature. This temperature dependence is less than that for both unoriented PET and typical amorphous polymers above Tg. It is about the same as that for oriented nylon 66 and unoriented glassy poly(methyl methacrylate). The isothermal modulus has the same time dependence as that of the unoriented PET; however, it is a factor of 3.3 larger. The modulus curve is almost identical in both shape and magnitude with that of oriented nylon 66. However, a temperature of 82°C. is required to place the viscoelastic dispersion region of PET at the same time scale as nylon 66 at 25°C. This temperature increase is the major difference in viscoelasticity between these two oriented polymers.
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    Temperature dependence of photoelastic properties of crosslinked amorphous polyethylenes (1968)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 1183-1202 
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    Keywords: Physics ; Polymer and Materials Science
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    Notes: Crosslinked samples of polyethylene were prepared by electron irradiation of both high- and low-density polymers in the crystalline state. A further crosslinked sample was obtained by curing a high-density polyethylene by reaction with dicumyl peroxide at 180°C. The stress-strain-birefringenece relations were obtained on specimens cut from these samples at temperatures between 130 and 250°C. All samples showed a substantial decrease in stress-optical coefficient with increasing degree of crosslinking and with increasing temperature. The stress-optical properties at each temperature were extrapolated to zero degree of crosslinking to give quantities characteristic of the Gaussian network. Comparison of these properties with the theory of networks of rotational isomeric chains with both independent and interdependent rotation allows estimates to be obtained for (1) the trans-gauche energy differences in rotation around skeletal bonds and (2) the difference in principal optical polarizabilities for the CH2 group in the elastomeric state. This latter quantity is shown to be more nearly given by Denbigh's than by Bunn and Daubeny's bond polarizability values.
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    Role of diffusion in gel permeation chromatography (1968)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 1217-1226 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: A theory is developed that describes the diffusion of solute into the gel particles during a gel permeation chromatographic experiment. The particles are treated as homogeneous spheres of radius a, into which diffusion takes place with diffusion coefficient Ds. The concentration in the mobile phase at any level at any time is supposed to be uniform throughout the cross-section of the column. It is shown that in the usual columns the effect of diffusion in the mobile phase is unimportant. A determinative quantity in the process is the parameter a2/Dst, where t is the time. For large values of a2/Dst an explicit expression for concentration versus time in the mobile phase at the end of the column is derived [eq. (26) and Fig. 1]. It shows a relatively long tail at large efflux volumes V, where the concentration varies at V-3/2. For arbitrary values of a2/Dst the first three moments of the concentration versus time curve are calculated [eqs. (33)-(37)]. Pronounced skewness of the curve is found unless a2/Dst is small.
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    Small-angle x-ray diffraction studies of plastically deformed polyethylene. II. Influence of draw temperature, draw ratio, annealing temperature, and time (1968)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 1273-1282 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: The angular dependence of scattering intensity of drawn polyethylene (PE) was investigated with a small-angle Kratky camera. At constant drawing temperature the intensity drops drastically with increasing draw ratio; however, the position and the half-width of the first maximum remain nearly unchanged. The drop in intensity can be explained only by a reduction of effective electron density difference between amorphous and crystalline components. The latter contains more vacancies, and the former contains more and better packed tie molecules. This increases the average density of the amorphous layer and decreases that of the crystalline component. As the temperature of the drawing increases, the draw ratio attainable at the applied draw rate drops and the intensity of scattering and the long period rapidly increase. In addition, a second-order maximum appears, indicating a better order of lamellar stacking, in good agreement with electron microscopy. The first annealing effect is an extremely rapid increase in scattering intensity and long period. The subsequent increase is rather slow and proportional to the logarithm of annealing time. The long period in such an experiment is independent of the draw ratio; however, the scattering intensity depends on it quite strongly even after prolonged annealing.
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    Relaxation characteristics and intrinsic birefringence and viscosity of polystyrene solutions for a wide range of molecular weights (1968)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 1331-1347 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A comparison is made between measurements on polystyrene solutions and the relaxation characteristics and intrinsic birefringence and viscosity given by the theory for the flexible Gaussian chain of variable number of segments and with internal viscosity and internal hydrodynamic interaction. This is done in order to determine the applicability of the theory to polymers over a wide range of molecular weights, including the low molecular weight range in which there may be conflict with the theoretical assumption of chains having a large number of segments. The longest, terminal relaxation time and the number of chain segments are determined from measurements of the frequency dependence of oscillatory flow birefringence while the intrinsic birefringence and viscosity are determined from steady flow measurements. The range of molecular weights studied is from approximately 900 at 106. It is found that the segment weight is approximately 1000 and the number of segments is in direct proportion to the molecular weight for the range from 1 to 1000 segments. The terminal relaxation time has a molecular weight dependence of the type given by the theory but with better agreement for higher molecular weights. While the measured dependences of the intrinsic viscosity and birefringence are in agreement with theory for molecular weights greater than 5 × 104, they deviate significantly for molecular weights below 1 × 104. The ratio of the intrinsic birefringence to intrinsic viscosity, which in theory is a constant independent of molecular weight, is found to change at the lower molecular weights.
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    Dielectric relaxations and electrical conductivities of poly(alkyl methacrylates) under high pressure (1968)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 1401-1418 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Dielectric properties of four methacrylate polymers (methyl, ethyl, n-butyl and n-octyl) were studied in the frequency range 0.0001 cps-300 kcps at temperatures above and below the glass transition temperature and at various pressures up to 2500 atm. At temperatures well above Tg a single relaxation peak (α′ peak) was observed in the case of the higher n-alkyl methacrylates. However, this peak was split into two peaks, α and β, with decrease in temperature or increase in pressure. The molecular motions corresponding to the α and the β relaxation processes are the micro-Brownian motions of amorphous main chains and of flexible side chains, respectively. From the temperature and the pressure dependence of the average dielectric relaxation time of these polymers the single relaxation process (the α′ process) was attributed to the micro-Brownian motion of the main chain coupled with that of the side chain. The effects of temperature and pressure on the d.c. conductivity of these polymers were also studied.
    Additional Material: 18 Ill.
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    Sedimentation transport method for determination of molecular weight distributions (1968)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 1457-1479 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The sedimentation of the system polystyrene-cyclohexane at the Flory temperature has been studied with emphasis on the effects of pressure as well as concentration. The relation between the molecular weight M and the limiting sedimentation coefficient s00, is found to be s00 = 1.50 × 10-15 M1/2 (sec.) The concentration dependence parameter ks has the form, ks = k′M1/2 = k″s00 with k′ = 4.5-5.5 × 10-4. However, a rather unexpected dependence of ks on the rotor speed is also found. A procedure is proposed for deducing solute molecular weight distributions from boundary spreading data in sedimentation transport experiments, a so-called “single concentration” method, requiring only one sedimentation run. Application to several polystyrenes (in cyclohexane at 35°C) with narrow, broad, and very broad distributions demonstrates the feasibility of the procedure. Comparisons are made with data from elution chromatography and gel permeation chromatography. The GPC method predicts somewhat broader distributions than those obtained by the other two methods.
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    Infrared spectra of polymer solutions. I. Conformational stability of isotactic polymer chains in solution (1968)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 1493-1508 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The infrared spectra of isotactic polystyrene, polypropylene, and poly-p-chlorostyrene were measured in dilute solutions or gels at various temperatures ranging from room temperature to -100°C. For isotactic polystyrene and polypropylene, all the absorption bands characteristic of the helical conformation of the molecules increase in intensity with decreasing temperature, and show intensities at low temperature as strong as in the highly crystallized samples. This suggests that the molecules can assume very regular conformations even in solution. Similar temperature dependence of the spectra was observed for a homogeneous gel of isotactic poly-p-chlorostyrene, which is believed to be noncrystalline. These experimental facts lead to the conclusion that the stability of the TG type helical conformation of these isotactic polymers may be ascribed to the intramolecular forces within a molecule. The fact that these spectral changes are reversible has permitted a thermodynamic treatment of the conformational regularity in solution on the basis of the infrared data. The temperature dependence of the absorption intensities has been interpreted quantitatively by a simple statistical mechanical model, and the enthaply and the entropy differences between the helical and the random states of the monomeric residue in the molecular chain have been estimated.
    Additional Material: 12 Ill.
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    Huggins constant k′ for flexible chain polymers (1968)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 1535-1549 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The Huggins constant k′ in the expression for the viscosity of dilute nonelectrolytic polymer solutions, η = η(1 + [η] c + k′[η]2c2 + …), is calculated. For polymers in the theta condition, k′ is estimated to be 0.5 〈 kθ′ ≤ 0.7. For good solvent systems, the Peterson-Fixman theory of k′ has been modified; the equilibrium radial distribution function in the original theory is replaced with a parametric distribution for interpenetrating macromolecules in the shear force field. Comparison of the modified theory with experimental k′ for polystyrenes and poly(methyl methacrylates) of different molecular weights in various solvents shows good agreement. An empirical equation which correlates the Huggins constant k′ and the viscosity expansion factor αη for polymers has been found to coincide well with the modified theory.
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    Modified Zimm-Crothers rotating-cylinder viscometer (1968)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 1555-1560 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1968.160060812
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    Excluded volume effect of linear polymer molecules (1968)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 1607-1612 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: An approximate closed expression for the excluded volume effect of linear polymer molecules is developed with the aid of a uniform expansion model of perturbed chains. The linear expansion factor α for the end-to-end distance is given by (α3 - 1) + (3/8) (α5 - α3) = (5/2)z where z is the excluded volume parameter. This equation is numerically close to the Ptitsyn equation in the ordinary range of α; i.e., for 1 ≤ α ≤ 2.
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    Structural studies of polyethers. IV. Structure analysis of the polyoxymethylene molecule by three-dimensional fourier syntheses (1967)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 63-81 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Detailed structure analysis of the polyoxymethylene molecule was carried out by the method of three-dimensional Fourier synthesis. The diffraction data were measured on a highly ordered polyoxymethylene sample prepared from a single crystal of tetraoxane by solid-state radiation polymerization. By assuming the anisotropic thermal factors for the oxygen and carbon atoms and taking into account the contribution of the hydrogen atoms, good agreement between the observed and calculated structure factors was obtained; the R factor is 8.8%. The distance between the oxygen atom and the helix axis r(O) = 0.671 A. is slightly shorter than r(C) = 0.691 A. The bond distance C—O = 1.421 A., the angle ∠COC = 112°24′, and ∠OCO = 110°49′. All the internal rotation angles of the skeletal bonds are 78°13′. It is deduced from the experimental results that each crystallite of polyoxymethylene is composed of only one type of helix, right-handed or left-handed.
    Additional Material: 8 Ill.
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    Effects of temperature and water on the γ → α crystalline transition of nylon 6 caused by stretching in the chain direction (1968)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 1317-1329 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The effects of temperature and water on the crystal transition of nylon 6 from the γ phase to the α phase, which is caused by stretching along the chain direction, were investigated. The γ-phase fibers with high crystallite orientation were stretched at constant load under various conditions. An inversion of the effect of water on the transition occurs at about -60°C. Stretching in the wet state is more effective for the transition at higher temperature. In contrast, at low temperatures water in the crystalline regions actsasa cohesive agent for the chains and increases the activation energy for the transition. Thus, dry stretching is more effective than wet stretching at very low temperature. The fraction of transformed α-phase crystallites increases abruptly over a narrow range of stress. Thus the critical stress can be determined for the transition. The critical stress changes appreciably with temperature; the higher the temperature, the lower the critical stress. The relation between stretching temperature and critical stress was analyzed by Flory's equation for the shift of transition temperature by stress. About 220°C. was estimated as the zero-stress transition temperature. The heat content of the γ-phase crystal was estimated to be smaller by 500 cal./mole than that of the α-phase crystal. This result suggests that the free energy of the γ-phase crystal is lower than that of the α-phase crystal at temperatures lower than the transition point. The irreversible strain of a sample in which the crystal transition has taken place is very small at low temperature. This small extension of the sample is evidence that the γ → α transition produced by stretching along the chain axis is a crystal-crystal transition.
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    Low-frequency losses in rubbers cross-linked in the presence of diluent (1968)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 1371-1379 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Measurements of the complex shear compliance have been made from 0.1 to 7 cycles/sec. and from -5° to 45°C. on several samples of natural rubber cross-linked by dicumyl peroxide in the presence of a diluent oil (volume fraction of rubber, v2, = 0.63 and 0.76) which was subsequently extracted. The properties of the extracted vulcanizates were compared with those having the oil still present and with those of conventional undiluted vulcanizates. Measurements of the diffusion coefficient of radioactively tagged n-hexadecane in trace amounts through the polymer structure were also made both before and after extraction of the oil. The diffusion coefficient was higher in the presence of the oil by an amount consistent with the Fujita theory for concentration dependence of diffusion rate based on free volume considerations. The low-frequency mechanical losses (reduced to 25°C. by the method of reduced variables), as measured by the loss tangent, were shifted to higher frequencies by the presence of oil to a much larger degree than would be expected from the difference in local mobility gauged by the diffusion coefficient. The equilibrium modulus, derived by extrapolation to zero frequency, was diminished by the presence of oil to a greater extent than the factor of v2⅓ expected from the simple theory of rubberlike elasticity. The low-frequency losses in the extracted vulcanizates were smaller than those in conventional vulcanizates with comparable degrees of cross-linking; the differences are attributed to differences in network topology.
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    URL: http://dx.doi.org/10.1002/pol.1968.160060713
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    Relation of the decay of free radicals in irradiated polyethylene to the molecular motion of the polymer and the configurations of the free radicals (1968)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 1435-1449 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Decay reactions of the free radicals produced in irradiated polyethylene (high-density and low-density materials) were examined in connection with the molecular motion of the matrix polymer. Three temperature regions, in which the free radicals decay very rapidly, at around 120, 200, and 250°K, were designated TA, TL, and TB, respectively. The decay of the free radicals at these temperatures had activation energies in high-density polyethylene of 0.4 kcal/mole for TA, 9.4 kcal/mole for TL, and 18.4 kcal/mole for TB. In low-density polyethylene these quantities were 0.7 kcal/mole for TA, 23.1 kcal/mole for TL, and 24.8 kcal/mole for TB. Comparison of time constants for the decay reactions and for molecular motion of the matrix polymer indicate that the decay in TA and TB is closely related to molecular motion in the amorphous regions of the polymer. The decay of the free radicals at TL in high-density polyethylene is due to molecular motion associated with local mode relaxation at lamellar surfaces, while that of low-density polyethylene is due to local mode relaxation in the completely amorphous region. Steric configurations of the free radicals which decay in the respective temperature regions were also investigated.
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    Annealing experiments on drawn nylon 66 fibers (1968)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 1527-1533 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Drawn, nylon 66 yarns have been annealed in oil under relaxed conditions. Shrinkage and tensile modulus were measured and the yarns were examined by wide- and small- angle x-ray diffraction. The results are similar to those obtained by Dismore and Statton, but there are significant differences. The data indicate a model for a drawn nylon 66 fiber in which substantial amounts of folds remain.
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    Structure of poly(ethylene oxide) complexes. II. Poly(ethylene oxide)-mercuric chloride complexPaper presented in part at the 15th Annual Meeting of the Society of Polymer Science (Japan) at Nagoya University, 1966. (1968)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 1509-1525 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The structure of the crystalline complex of poly(ethylene oxide) with mercuric chloride, whose composition is (CH2CH2O)4 · HgCl2, has been determined by x-ray diffraction. The unit cell is orthorhombic with the dimensions of a = 13.55 Å, b = 8.58 Å, and c (fiber axis) = 11.75 Å, and the unit cell contains 4 HgCl2 molecules and 16 CH2CH2O units. Four chains pass through the lattice and four monomeric units are contained in the fiber identity period. The space group is Ccmm-D2h17, Ccm21-C2v12, Cc2m-C2v16 or C2221-D25. The positions of Hg and Cl atoms have been determined by the Patterson function synthesized by the use of intensity data of the fiber sample, and the molecular conformation of poly(ethylene oxide) has been determined by examining the space not occupied by mercuric chloride molecules in the crystal lattice. The conformation of polyethylene oxide in the complex has been found to be the form of T5GT5G; that is, where G and G mean the right- and left-handed gauche forms, respectively. This molecular structure has been confirmed further by the results of the Fourier syntheses by using the more accurate data refined by the intensity measurements with a diffractometer on the powder sample. The bond length between Hg and Cl in the complex (2.30 Å) is a little longer than that of HgCl2 in the crystal (2.25 Å). This is consistent with the fact that the infrared absorption band associated with the antisymmetric stretching vibration of HgCl2 shifts to 353 cm-1 in the complex from 367 cm-1 in the crystal. It was also found that another type of complex, giving a different infrared spectrum and x-ray diffraction pattern, was obtained when the original complex was soaked much longer in a saturated ether solution of HgCl2.
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    Development of gel permeation chromatography for polymer characterization. II. Universal calibration (1968)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 1579-1591 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: GPC appearance volumes have been determined for a series of linear polyethylene, polystyrene, and polybutadiene fractions (Mw/Mn 〈 1.1) in trichlorobenzene at 130°C. and for the latter two series in tetrahydrofuran at 23°C. A polymer-type independent relationship between appearance volumes and the equivalent hydrodynamic radii of the polymer molecules has been demonstrated. The equivalent hydrodynamic radius is calculated from intrinsic viscosity data. It is proposed that this relationship can be used to construct a universal GPC calibration curve for polymers that assume a spherical conformation in solution. Methods for applying the universal curve to the determination of molecular weight averages and molecular weight distribution are described. In addition, a method is outlined by which the universal calibration curve can be empolyed for determining number-average Mark-Houwink constants from polydisperse samples.
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    Frequency dependence of intrinsic viscosity of macromolecules with finite internal viscosity (1967)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 179-193 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: In order to explain the observed nonvanishing limiting value of dynamic intrinsic viscosity of polymer solutions at ω = ∞ one has considered the necklace model with finite resistance to the rate of coil deformation introduced long ago by Cerf for the study of gradient dependence of intrinsic viscosity and streaming birefringence. The calculation need not take into account change of hydrodynamic interaction as a consequence of coil deformation because the experimental data are always either obtained at very low gradient or extrapolated to zero gradient so that in the experiment the macromolecule has the same conformation as in the solution at rest. The model indeed yields a finite [η]′ω = ∞ in good agreement with experiments on polystyrene in Aroclor. According to the theory [η]′ω = ∞/[η]0 decreases with increasing molecular weight as M-1 and M-1/2 for the free-draining and impermeable coil, respectively. The absolute limiting value [η]∞′, therefore turns out to be nearly independent of M, at least for small values of internal viscosity. From the observed value [η]∞′/[η0] one can obtain the coefficient of internal viscosity of the macromolecule. The value for polystyrene in Aroclor calculated from dynamic experiments on rather concentrated solutions is close to that derived by Cerf from streaming birefringence observations of polystyrene in a series of solvents of widely differing viscosity.
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    A concise polymer crystal genealogy (1967)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 225-229 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 5 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1967.160050118
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    Radiation-induced catalytic polymerization. I. Theory (1967)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 211-223 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The kinetics of radiation polymerization on a solid catalyst is discussed, under the condition that only linear termination of the chain takes place. All the kinetic equations are balance equations of particles of each type adsorbed by unit mass of the catalyst, and this makes it possible to account for the effect on the kinetics of the time dependence of the magnitude of the part of its surface on which the reactions we are considering may take place. Integro-differential equations are used for calculating the molecular weight distribution of the resulting polymer; this ensures higher accuracy of the formulas obtained than when differential equations are used and makes it possible to eliminate a number of limitations generally involved in the transition to differential equations. An expression has been found for the molecular weight distribution of the polymer product which allows for the possibility of radiation-induced catalytic polymerization on the resulting adsorbed polymer. Expressions have been derived for the average molecular weight and yield (weight and molecular) of the polymer formed. Asymptotic formulas have been obtained (for large irradiation times) for all the above values. The conclusions that can be drawn concerning the mechanism of the process based on a comparison of the formulas obtained with kinetic curves plotted from experimental data are given. It is shown how such a comparison can be utilized for calculating the rate constants for polymerization and chain termination reactions.
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    Dynamic mechanical properties of a gel of cellulose nitrate in diethyl phthalate: Reduced variable analysis in terms of amorphous and crystalline phases (1967)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 195-210 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A phenomenological theory is presented to extend the method of reduced variables for the effects of both temperature and changing degree of crystallinity on the linear viscoelastic properties of solutions of crystalline polymers. The vertical and the horizontal shift factors, which are both obtainable in the course of analysis of the experimental data, are correlated with the concentration of the solution and the volume fraction of the crystalline phase, and the fractional free volume of the system, respectively. Dynamic mechanical properties of a gel of cellulose nitrate (nitrogen content, 12.6%) in diethyl phthalate with a nominal concentration of 18% by weight were obtained in the transition region from glasslike to rubberlike consistency and also in the rubbery plateau region by employing the Fitzgerald apparatus and a freely oscillating torsion pendulum over the temperature range from -49 to 65°C. Application of the new reduction method to the experimental data was found to be quite successful, and it was shown that in general the degree of crystallinity in the system (and hence also the concentration of polymer in the amorphous phase) can depend on both temperature and thermal history. The dynamic mechanical data of a gel of different nominal concentration (23% by weight) previously obtained by Plazek were reanalyzed in terms of the method herein given.
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    Intrinsic viscosity of homopolymers and graft copolymers in solvent mixtures (1967)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 230-234 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1967.160050119
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    Macromolecules in solution (high polymers, volume XXI). HERBERT MORAWETZ. Interscience, New York, 1965. xvi + 495. $16.50 (1967)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 235-236 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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    URL: http://dx.doi.org/10.1002/pol.1967.160050120
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    Solution properties of polystyrene-polybutadiene block copolymers (1968)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 2051-2066 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Dilute solution viscosity and osmotic pressure measurements were performed on polystyrene (PS), polybutadiene (PB), polystyrene-polybutadiene (SB) diblock and polystyrene-polybutadiene (SBS) triblock copolymers. Anionic polymerization was used in such a way that the molecular weight of the PS block was kept constant (ca. 10 000), while the molecular weight of the PB block varied from 18000 to 450000. The measurements were carried out at a fixed temperature of 34.20°C in three solvents, namely toluene, a good solvent for PS as well as for PB, dioxane, which is a good solvent for PS and almost a theta solvent for PB, and cyclohexane, which is nearly a theta solvent for PS and a good solvent for PB. The compositions of SB and SBS, as derived from kinetic data agree with ultraviolet measurements in CHCl3 solutions. The viscosity and osmotic pressure results indicate that the properties of SB and SBS are similar. Their intrinsic viscosities and second virial coefficients can be calculated from their chemical compositions, molecular weight, properties of parent polymers, and values of the interaction parameter \documentclass{article}\pagestyle{empty}\begin{document}$\bar \beta _{{\rm SB}}$\end{document} between styrene and butadiene units, for molecular weights not exceeding approximately 105. The magnitude of \documentclass{article}\pagestyle{empty}\begin{document}$\bar \beta _{{\rm SB}} $\end{document} varies with the solvent. The results suggest that the domains of the PS and PB blocks overlap to a great extent.
    Additional Material: 4 Ill.
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    Recording microdilatometer for the measurement of polymer crystallization rates (1967)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 391-393 
    Details
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1967.160050213
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  • 164
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    Configuration and hydrodynamic properties of fully acetylated salep glucomannan (1967)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 361-375 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The polysaccharide of salep orchid tuber was shown to be a glucomannan with a glucose/mannose ratio of 2.6 and an acetyl content of 2.1%. After extraction from the powdered root with water, the triacetate derivative was prepared and its configurational and hydrodynamic properties examined. The polymer yielded a series of fractions from 615 to 4170 in weight-average degree of polymerization. Light-scattering, viscosity, and osmometry experiments were conducted. Intrinsic viscosity results were interpreted according to the hydrodynamic theory of Eizner and Ptitsyn resulting in a value of ζ/η0 = 20 ± 6 A. for the ratio of monomeric friction coefficient to solvent viscosity and a corresponding value of a = 55 ± 4 A. for the persistence length, closely similar to those reported for other β-1,4-linked polysaccharides. The theoretical Flory coefficient increased with increasing molecular weight but was less than the limiting value of Φ0 = 2.86 × 1023 mole-1. The dependence of the light-scattering radius of gyration of the glucomannan polymer on the contour length showed that the configuration of the heteropolymer was similar to that of other β-1,4-linked polysaccharides which have only glucose or mannose in the main chain. Calculated radii of gyration based on the Porod-Kratky persistence length were found to be smaller than radii found by light scattering on the fractions.
    Additional Material: 7 Ill.
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    Some optical and mechanical properties of poly(vinyl chloride) (1967)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 583-596 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The optical and mechanical properties of poly(vinyl chloride) film were examined by observing both the stress and birefringence during stretching at constant rate, during relaxation at constant length and during a dynamic birefringence experiment. Experiments were also done by varying the temperature at constant length. The changes in birefringence are interpreted in terms of changes in negative distortional birefringence, changes in positive orientation birefringence, and possible reversible changes in birefringence with temperature arising from conformational changes in the polymer chain and changes in the contribution of birefringent crystals.
    Additional Material: 10 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1967.160050315
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  • 166
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    Morphology of polypropylene crystals. I. Dilute solution-grown lamellar crystals (1967)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 597-613 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The dependence of crystalline morphology of isotactic polypropylene crystallized from dilute solutions on its molecular weight and growing conditions and the mechanism of crystal growth were studied by electron microscopy and electron diffraction. Lathshaped lamellar crystals 150-300 A. in thickness are obtained from fractionated polypropylene powders of Mw (average molecular weight) = 600,000 and 240,000, but not from the samples of Mw = 82,000 and 44,000, by means of isothermal crystallization at 130°C. for 20 hr. in dilute α-chloronaphthalene solution (0.005 wt.-%). Precipitation of the fractionated polypropylene sample of Mw = 82,000 from a dilute solution of carbitol gives typical dendritic crystals under the same isothermal crystallizing conditions as mentioned above. The mode of chain folding in these crystals based on the orientation and the crystal structure of the lamellar crystals agrees with that proposed by Sauer, Morrow, and Richardson. From the morphological observations, the mechanism of growth pertinent to polypropylene lamellar crystals is presumed to be as follows: fibrils at first aggregate, then the molecular chains are folded to form small lamellae, and then these small lamellae accumulate compactly to grow to large, lath-shaped, lamellar crystals.
    Additional Material: 12 Ill.
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  • 167
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    Selective polymeric effects on solvent NMR relaxations (1967)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 697-704 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Measurements of the spin-lattice relaxation times (T1) of solvent protons have been performed on systems containing mixed solvents with and without polymer. It has been found that the motion of solvent is selectively affected by polymers present in the system. Polyisobutylene (10%) in mixed solvents of carbon tetrachloride (or cyclohexane) and dichloromethane at various proportions produces little effect on T1 values of dichloromethane, but it affects significantly the T1 values of cyclohexane; whereas poly(methyl methacrylate) (10%) in carbon tetrachloride and dichloromethane (or acetone) selectively associates with dichloromethane (or acetone), resulting in an approximate 50% reduction of the T1 values for dichloromethane (or acetone). In systems of poly(methyl methacrylate) and three mixed solvents of carbon tetrachloride, dichloromethane, and cyclohexane, the polymer (10%) has a negligible effect on the T1 values of cyclohexane, but brings about a 50% reduction of the T1 values of dichloromethane. These phenomena are discussed in terms of local selective interactions between the solvent molecules and the polymeric chain segments.
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    Configurational enthalpy of polystyrene (1967)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 705-710 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Recent precision measurements of the heats of combustion of atactic and isotactic polystyrene permit an unequivocal calculation of the enthalpy difference in the bulk amorphous forms of the two isomers of this polymer. Contributions to this quantity arise mainly from the differences in nonbonded interactions in the two configurations but may also contain terms relating to higher energy conformations and to intermolecular interactions. The thermochemical and NMR data of specific polymers and of simple molecules are discussed in a comparison with model compound calculations. The thermochemical method has potentially important applications in studying molecular interactions in stereoregular polymers.
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    Energy contents of amorphous polystyrene with different thermal historiesSome of these results were presented at the International Congress on Macromolecular Chemistry, Prague, 1965. (1967)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 743-749 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The Tian-Calvet microcalorimeter has been used to measure the heat of solution of atactic polystyrene in toluene at 30°C. By using a special technique for polymer sample preparation, it has been possible to measure directly the difference in conformational energy of the polystyrene chain at different temperatures, from 30 to 100°C. and to calculate its contribution to the specific heat.
    Additional Material: 1 Ill.
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    Models of spherulite deformation taking into account changes in volumePaper presented in part at the 36th Annual Meeting of the Society of Rheology, Cleveland, Ohio, October 1965. (1967)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 711-742 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A general method is presented for taking into account changes in volume in several types of calculations concerned with spherulite deformation in semicrystalline polymers. The method is applicable at large strains for which the low-strain limiting form of the equation defining Poisson's ratio is no longer valid. Applications are made to calculations of the three crystal orientation functions for models of spherulite deformation based on those proposed by Wilchinsky, Stein et al., and Oda et al. The effects of changes in volume are considered in detail and are compared with previous results in which the volume change was neglected. Calculations of spherulite birefringence are considered in a similar manner, as are the equations for determining spherulite deformation by means of low-angle light-scattering measurements. Results indicate that in several cases details of deformation mechanisms previously proposed should be revised in light of the effect of the change in volume on the calculated orientation functions. The equations in each case are presented in terms of a parameter β, the square root of the third strain invariant of the deformation tensor. Results are presented in numerical form for many of the basic parameters. Equations for all such results are expressed in explicit form and, in most cases, are displayed graphically together with available experimental data.
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    Dynamic mechanical properties of aromatic, aliphatic, and partially fluorinated epoxy resins (1967)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 761-769 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The α, β, and γ transitions at temperatures between -200 and +100°C. of crosslinked aromatic and aliphatic epoxy polymers were determined from damping and shear modulus data, and compared with their fluorine containing analogs. Loci of segmental relaxation are suggested at various temperatures, and similarities between aliphatic and fluorocarbon segments, and polyethylene and polytetrafluoroethylene are discussed. Two systems of structurally similar monomers 2,2,3,3,4,4-hexafluoropentane diglycidyl ether-1,5 and 1,4-butane diglycidyl ether, and 2,2-bis(4-glycidyl phenyl ether)hexafluoropropane and 2,2-bis(4-glycidyl phenyl ether) propane were polymerized with the aid of two diamine curing agents, namely, ethylenediamine and m-xylylenediamine. Polymers of the aromatic diepoxides showed transitions with peaks at -56°C. and above +70°C. Three main peaks were registered for the aliphatic and fluorocarbon diepoxides: at -125 and at -100°C., at -56°C., and at 0°C. It is suggested that the Tg is affected by an interdependence of relaxation of all components of the polymer main chain.
    Additional Material: 10 Ill.
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    Apparatus for the measurement of the flow birefringence of polymer melts (1967)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 781-790 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A description is given of a modified cone-and-plate apparatus suitable for the measurement of the streaming birefringence of molten polymers. Some results are given of measurements on a polystyrene and a poly(dimethyl siloxane). Those on polystyrene are compared with solution measurements of the same material by use of the well-known Bueche-Harding parameter. Measurements on the silicone oil have been compared with measurements of the dynamic moduli on the same material, after ascertaining the validity of the stress-optical law for this system as well.
    Additional Material: 5 Ill.
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    Thermodynamic properties of polybutene-1 and butene-1 (1967)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 791-794 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1967.160050414
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    Strain birefringence of poly(vinyl alcohol) gels (1967)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 795-798 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1967.160050415
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    Measurement of concentration gradients in swelling crosslinked polymer beads (1967)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 799-816 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The concentration of solvent in the gel phase of a swelling polystyrene-divinylbenzene copolymer bead has been measured as a function of the radius by optical interference techniques. It is found that an appreciable gradient exists even shortly after the core disappears. Results are presented for two cases: a very lightly crosslinked bead that exhibits negligible birefringence while swelling, and a more tightly crosslinked network in which the birefringence must be considered. It is also found that the refractive index of the unswollen bead is considerably less than that found by extrapolation from the swollen state; this effect is reasonable when the “free volume” in the bulk polymer is considered.
    Additional Material: 15 Ill.
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    Birefringence dispersion in oriented polystyrene (1967)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 817-828 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The dispersion of birefringence in oriented amorphous polymers is discussed. It is shown that for polystyrene, the birefringence can be considered as the product of an orientation function and a function of the wavelength of the light. This leads to a method for expressing the birefringence dispersion as a function that is characteristic of the polymer. This function is determined for polystyrene, and from it the birefringence at infinite wavelength is found to be 11% lower than that measured with the mercury green line (5461 A.).
    Additional Material: 8 Ill.
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    Molecular dimensions of polydipropylsiloxamer (1967)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 829-838 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The molecular dimensions of polydipropylsiloxamer were studied by intrinsic viscosity measurements in toluene and in 2-pentanone. The relationships between the molecualr weight and the intrinsic viscosity were found to be: [η]25°C., toluene = 4.35 × 10-4 M0.58; [η]θ(10°C.), toluene = 1.09 × 10-3 M0.5; [η]θ(76°C.), 2-pentanone = 8.71 × 10-4 M0.5. This held reasonably well for molecular weights from 25,000 to 3000,000. The root-mean-square end-to-end length ratio, (r02/M)1/2 as calculated from the constant K, exceeds the free rotation value by approximately 100%. The disparity is greater than that found with polydimethylsiloxamer, indicating a lower degree of flexibility for the polydipropylsiloxamer. This is largely due to the short range steric interaction between near neighboring units of the chain. Gel permeation chromatography was also employed to demonstrate the lower degree of flexibility for polydipropylsiloxamer as compared with polydimethylsiloxamer.
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    Corresponding state relations for the Newtonian viscosity of polymer solutions. II. Further systems and concentrated solutions (1967)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 853-874 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: In earlier work we have indicated a superposition principle for moderately concentrated mixtures (c ≲ 2/[η]) in good and poor solvents. By an examination of data on a number of vinyl polymers and cellulose derivatives in good as well as poor solvents, the validity of this principle is extended to concentrated solutions (c ≲ 50%). The characteristic concentration factor γ is proportional to M-a1 over the whole concentration range, with 0.47 ≤ a1 ≤ 1.10 being larger for good than for poor solvents, the result obtained earlier. Significant deviations from this relationship are noted in good solvents for those low molecular weights at which deviations from the usual intrinsic viscosity relationship occur. This may be related to the expansion factor of the polymer coil. On the basis of these results, the concentration and molecular weight dependence of the viscosity in the concentrated solution can be related to each other in terms of the parameter a1 and thus to thermodynamic characteristics. In this manner a bridge between the relatively dilute and concentrated regions is established. Currently used semiempirical expressions are analyzed in terms of these results. For the polystyrene-cyclohexane systems and θ - 9 ≦ T ≦ θ + 3, γ can be identified with the critical concentration for phase separation. Provided an “entanglement” concentration ce exists, in the neighbourhood of which the concentration dependence of the viscosity changes reapidly, γ can alternatively be shown to be proportional to ce, or ce ∝ M-a1. The temperature reduction scheme suggested earlier remains to be investigated.
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    Dependence of viscosity of concentrated polymer solutions upon molecular weight and concentrationPresented at the International Symposium on Macromolecular Chemistry, Tokyo and Kyoto, October 4, 1966. (1967)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 899-913 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: Molecular weight M and concentration c dependencies of the zero-shear viscosity (η) were measured over wide ranges of M and c for concentrated solutions of linear and branched poly(vinyl acetate) as well as of polystyrene under θ conditions. The log η versus log M and log η versus log c curves for a given system can be superposed by the horizontal shift along the abscissa, giving smooth master curves. From the shift factors the ratio of two exponents β and α, which appear in the following equation, can be evaluated: η = K′(cρ)αMβ, where ρ is the density of the solution and K′ is a constant at constant temperature. The evaluated values of β/α for the systems under θ conditions are equal to or very close to 0.50 as was anticipated from the previous work. The above superposition method was also applied to available viscosity data, and it was found that β/α had a good correlation with a in [η] = KMa. This indicates that the individual molecules in concentrated solutions maintain the same individuality as in dilute solutions, and might be a positive support to the packed sphere model proposed previously by the authors. The effect of solvent on the molecular weight and the concentration dependencies of viscosity was also discussed.
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    Synthetic thermally reversible gel systems. II (1967)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 915-927 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The homopolymer and many of the copolymers of N-acrylylglycinamide yield thermally reversible gels in water. These systems are uniquely suitable for studying synthetic photographic gelatin substitutes and for understanding the mechanism of the gelation process. Polymerization of N-acrylylglycinamide has been studied under a variety of conditions. The homopolymer is aggregated in dilute aqueous solution and probably molecularly dispersed in 2M thiocyanate solution. At concentrations of several per cent, in water, thermally reversible gels are formed whose melting points rise with increasing concentration and increasing molecular weight. The heat of gelation crosslinking has been calculated to be -8.8 kcal./mole of crosslinks. Introduction of small amounts of carboxyl groups into the polymer raises the melting points of the aqueous gels. The effect of various organic and inorganic reagents on gelation is presented. The ability to prepare copolymers which can be flocculated has been demonstrated as well as the usefulness of the monomer in certain types of photoresist systems. Copolymerization with acrylic acid and β-aminoethyl vinyl ether has been studied, and the r1 and r2 values for these systems have been calculated as well as Q and e values for N-acrylylglycinamide.
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    Configurations of the free radicals in irradiated polypropylene and the relation of their decay reactions to the molecular motion (1967)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 929-938 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Free radicals produced in irradiated polypropylene were studied by the electron spin resonance method. Two temperature regions in which the free radicals decay rapidly were found at around 170°K. and 260°K. The first temperature region corresponds to the γ-dispersion of polypropylene and the second to the β-dispersion. Steric configurations of the free radicals were investigated, and it was concluded that the free radicals trapped in polymer, conformation of which is appreciably twisted from the stable 31-helical structure, decay with small-scale motion of the matrix polymer. The decay of free radicals trapped in polymer of less twisted conformation is associated with the large-scale motion of the matrix polymer. Activation energies of decay were found to be 11 kcal./mole at the lower temperature and 48 kcal./mole at the higher temperature. Time constants of the decay reactions were compared with those for molecular motion of the matrix, with results reflecting the relations of the decay of the polymer radicals to molecular motion in the matrix.
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    Deformation of polybutene-1 spherulites (1967)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 939-955 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The deformation of fresh and aged polybutene-1 spherulitic samples has been investigated by microscopic observation, interferometry, studying macroscopic and spherulitic birefringence changes, and study of light-scattering patterns. The spherulite deformation is not affine, the microscopic deformation ratio being less than the macroscopic deformation ratio of the sample and greater in the equatorial regions of the spherulite than in the polar regions. The deviation from affine deformation is less for fresh spherulites than for the aged, where void formation occurs in the equatorial part of the spherulite. This gives rise to large scattering by this part of the spherulite and to form birefringence. The spherulite birefringence and its change with elongation is dependent upon the degree of aging of the sample. The spherulite birefringence is more negative for the aged sample. In the polar regions of the spherulite, this negative birefringence decreases and turns positive at higher elongations, characteristic of a reorientation of the crystals with their optic axes turning from being perpendicular to parallel to the spherulite radius. The spherulite birefringence in the equatorial direction becomes somewhat more negative on stretching a fresh sample but less negative on stretching an aged one. Spherulite distortion and orientation changes are apparent from the light-scattering patterns of films possessing small spherulites. The changes in Vv and Hv scattering patterns upon stretch are different for the fresh and aged samples. The Vv patterns of the fresh samples decrease in intensity with time after stretching a fresh sample with the Hv patterns do not.
    Additional Material: 15 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1967.160050511
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  • 183
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    Heat of fusion of polyethylene (1967)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 987-988 
    Details
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1967.160050514
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  • 184
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    An atomistic approach to the nature and properties of materials. J. A. PASK, Ed. Wiley, New York, 1967. xi + 477. $19.95 (1967)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 989-989 
    Details
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1967.160050515
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  • 185
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    Polyelectrolyte behavior and conformation of poly-L-methionine S-methylsulfonium salts in aqueous solution (1967)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 1013-1028 
    Details
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The influence of the species of counterion on the polyelectrolyte behavior and the conformation of poly-L-methionine S-methylsulfonium salts in aqueous solution was studied by viscometric, electrochemical, and optical measurements. The degree of binding of small counterions to charged polyions increases in the sequence: chloride ≲ bromide 〈 iodide 〈 thiocyanate. The conformations of chloride and bromide salts are independent of polymer concentration. On the contrary, iodide and thiocyanate salts indicate a conformational transition, probably from a random-coil conformation to an intermolecularly stabilized β-form, with the increase of polymer concentration. The results suggest the existence of a strong specific interaction between counterion and macroion in iodide and thiocyanate salt solutions at high polymer concentration.
    Additional Material: 12 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1967.160050602
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  • 186
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    Investigation of the fold-surface problem in polyethylene single crystals with the nitric acid oxidation technique (1967)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 991-1012 
    Details
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Single-crystal preparations of polyethylene were treated with the selective oxidizing agent, fuming nitric acid. The degraded products were examined as regards layer thickness (by low-angle x-ray studies), chemical and weight changes, recrystallization and annealing treatments, and by broadline NMR, as part of a systematic investigation aimed at clarifying the nature of disordered material in single crystals. It emerges that there is a disordered-mobile region along the fold surface of the crystals in agreement with other parallel works along similar lines. In a more detailed analysis we can now decompose the nitric acid attack into components affecting the basal and side surfaces, respectively. Taking into account the recrystallization-annealing observations, we infer that the fold surface is heterogeneous with folds of more than one kind. These results were combined with a preliminary molecular weight distribution study by gel permeation chromatography. Taking into account all the available evidence, we are led to suggest a composite structure where surface looseness, coresponding to long loops and hairs, is superimposed on the more regular folded surface. This model is in the process of being tested. The problems concerning the assignment of a value to the amount of surface looseness are being discussed. In addition, a discontinuity in the thermal behavior of the crystals between 75 and 80°C. has been detected.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1967.160050601
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  • 187
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    Caractérisation des polymègres réaticuléas sous tension (1967)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 1029-1042 
    Details
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: This paper is devoted to the determination of the number of intermolecular bonds in a polymer crosslinked according to the following process: (1) crosslinking in the usual isotropic state, (2) additional crosslinking of the strained primary network. The Flory equation for swelling in solvents has been modified in order to take into account the oriented state of the initial network at the time of secondary crosslinking. The combination of this equation with those relating the modulus of elasticity and the dimensions of the relaxed sample to the deformation of the primary network at the time of secondary crosslinking leads to different possible evaluations of the number of intermolecular bonds. Their significance is discussed. The equations thus established are tested with natural rubber samples vulcanized according to the above-mentioned process. The validity of the number of crosslinks thus calculated is discussed; a partial degradation of the primary network occurs during the second crosslinking. Its influence is taken into account by using the approximated equations proposed by Flory. The efficiency of the vulcanizing agent (TMTD) is consequently shown to be practically independent of the deformation of the primary network at the time of secondary crosslinking.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1967.160050603
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  • 188
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    Gel permeation chromatography of polyethylene: Effect of long-chain branching (1967)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 1087-1101 
    Details
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The effect of long-chain branching on the size of low-density polyethylene molecules in solution is demonstrated through solution viscosity and molecular weight measurements on fractionated samples. These well-characterized fractions are analyzed by gel permeation chromatography (GPC), and it is shown that the separation of the polymer molecules by this technique is sensitive to the presence of long-chain branching. By using fractions of branched polyethylene possessing differing degrees of branching, one observes that a single curve is adequate in relating elution volume to molecular weight. This calibration curve is applied in the GPC analysis of a variety of commercial low-density polyethylene resins and it is shown, by comparison with independent osmometric and gradient elution chromatographic data, that realistic values for molecular weight and molecular weight distribution are obtained. The replacement of molecular weight M by the parameter [η]M as a function of elution volume, leads to a single relationship for both linear and branched polyethylenes. This indicates that GPC separation takes place according to the hydrodynamic volumes of the polymer molecules. The comparison of data for polyethylene and polystyrene fractions suggests that this volume dependence of the separation will be observed for other polymer-solvent systems.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1967.160050609
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  • 189
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    Ein Beitrag zur Darstellung von Alkalisalzen saurer Schwefelsäureester verschiedener Naphthol AS-Verbindungen (1965)
    New York, NY : Wiley-Blackwell
    Journal für Praktische Chemie/Chemiker-Zeitung 27 (1965), S. 99-107 
    Details
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Zwecks Bestimmung von Sulfatasen wird eine allgemein anwendbare Synthese für Naphthol AS-Sulfate und andere Arylhydrogensulfate beschrieben, die den gewünschten Reinheitsgrad der teilweise leicht hydrolysierbaren Substanzen gewährleistet. Als hauptsächlichstes Nebenprodukt entsteht wahrscheinlich die 1-Sulfosäure der Naphthol AS-Sulfate. Die erforderlichen Naphthol AS-Verbindungen werden nach bekanntem Verfahren über das 2-Oxynaphthoesäure-(3)-chlorid mit den entsprechenden Arylaminen hergestellt.
    Additional Material: 2 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/prac.19650270111
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  • 190
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    Zur Kenntnis des o-Vanillins. VI. Kondensationsreaktionen des 5-Carboxyvanillins (1965)
    New York, NY : Wiley-Blackwell
    Journal für Praktische Chemie/Chemiker-Zeitung 28 (1965), S. 99-107 
    Details
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Das nach unseren Untersuchungen aus o-Vanillin leicht zugängliche 5-Carboxyvanillin wurde einer Reihe von Kondensationsreaktionen mit methylenaktiven Verbindungen unterworfen. Die entsprechenden Zimtsäuren bzw. ω-Acetylstyrol-Verbindung wurden erhalten.Zum Zwecke der Untersuchung der Reaktionsfähigkeit von aromatischen Dialdehyden wurden die nach unseren Ergebnissen aus o-Vanillin oder seinen Alkyläthern leicht zugänglichen 4-Alkoxy-5-methoxyisophthalaldehyde der Kondensation mit Malonsäure nach KNOEVENAGEL unterworfen. Beide Aldehydgruppen reagieren unter Bildung von β-(2-Alkoxy-3-methoxyzimtsäure-5)-acrylsäuren.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/prac.19650280111
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  • 191
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    Use of cadmium acetate in quantitative separation of anions. Separation of arsenate, selenate, tellurate, selenite or tellurite from: (a) iodide and (b) per-rhenate (1965)
    New York, NY : Wiley-Blackwell
    Journal für Praktische Chemie/Chemiker-Zeitung 28 (1965), S. 134-136 
    Details
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: It has been shown that cadmium acetate can be used for the gravimetric separation of (a) iodide and (b) per-rhenate from arsenate, tellurate, selenate, tellurite or selenite.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/prac.19650280305
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  • 192
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    Heterocyclen aus Amino-ketonen. VI. 1.2.3-Trisubstituierte Indole aus N-alkylierten aromatischen o-Amino-ketonen und α-Halogendiketonen (1965)
    New York, NY : Wiley-Blackwell
    Journal für Praktische Chemie/Chemiker-Zeitung 28 (1965), S. 169-177 
    Details
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Durch basische Kondensation von N-alkyliertem o-Amino-acetophenon bzw. -benzophenon mit 1-Phenyl-3-brom-propandion-(1.2) entstehen in einstufiger Reaktion 1.3-dialkylierte 2-Phenylglyoxylyl-indole.
    Additional Material: 6 Tab.
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    URL: http://dx.doi.org/10.1002/prac.19650280309
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  • 193
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    Brom-Methoxylierung ungesättigter Fettsäuren (1965)
    New York, NY : Wiley-Blackwell
    Journal für Praktische Chemie/Chemiker-Zeitung 28 (1965), S. 199-208 
    Details
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Durch Einwirkung von N-Brom-succinimid und Methanol auf geometrisch-isomere Monoenfettsäuren(Öl-/Elaidin- und Eruca-/Brassidinsäure) bzw. ihre Ester (Ricinol-/Ricinelaidinsäure-methylester) entstehen bei Raumtemperatur innerhalb einer Stunde die entsprechenden diastereomeren brom-methoxylierten Fettsäuren bzw. Ester. Unter denselben Bedingungen werden Polyenfettsäuren (Linol- und Linolensäure) in Dibrom-dimethoxy-bzw. Tribrom-trimethoxy-stearinsäure übergeführt.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/prac.19650280312
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  • 194
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    Zur Kenntnis des o-Vanillins. V. 5-Carboxyvanillin und Derivate (1965)
    New York, NY : Wiley-Blackwell
    Journal für Praktische Chemie/Chemiker-Zeitung 28 (1965), S. 225-235 
    Details
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Ausgehend vom 5-Carboxyvanillin, das auf neuartige Weise aus o-Vanillinsäure mit Hexamethylentetramin synthetisiert wurde, sind durch Kondensationen mit Aminen 2-Hydroxy-3-methoxy-5-alkylazomethin-N-alkylbenzoesäureamide dargestellt worden. Mit Nitroparaffinen wurden aus 5-Carboxyvanillin sowie aus 5-Carbomethoxyvanillin die entsprechenden Nitroalkylene gewonnen.Zum Zwecke des Studiums der Reaktionsfähigkeit von aromatischen Dialdehyden wurden 4-Alkoxy-5-methoxy-isophthalaldehyde überwiegend mit Nitromethan zur Umsetzung gebracht, wobei beide Aldehydgruppen reagierten und substituierte 1,3-Bis-(β-nitrovinyl)-benzole erhalten wurden.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/prac.19650280501
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  • 195
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    Über die Darstellung von Indeno-[1.2]-imidazolen und Versuche zu ihrer Dehydrierung (1965)
    New York, NY : Wiley-Blackwell
    Journal für Praktische Chemie/Chemiker-Zeitung 28 (1965), S. 297-304 
    Details
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 2-Amino-(3-alkyl, -aryl)-indanon-(1)-hydrochloride werden mit Kaliumthiocyanat zu 2-Mercapto-indeno-[l, 2]-imidazolen umgesetzt, die sich mit RANEY-Nickel zu den Indeno-[l, 2]-imidazolen entschwefeln lassen. Dehydrierungen der Indeno-imidazole sowie des Indano-v-triazols führten nicht zu beständigen Benz-di-(tri)-azpentalenen.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/prac.19650280506
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  • 196
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    Peptide der p-Aminophenylessigsäure (1965)
    New York, NY : Wiley-Blackwell
    Journal für Praktische Chemie/Chemiker-Zeitung 27 (1965), S. 57-63 
    Details
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Es werden neue Peptide der p-Aminophenylessigsäure hergestellt. Dabei wurde die Peptidbindung einmal an der NH2-Gruppe und zum anderen an der COOH-Gruppe der p-Aminophenylessigsäure mit Hilfe der Chloracetylmethode und über die gemischten Anhydride geknüpft.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/prac.19650270106
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  • 197
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    Zur Kenntnis der Zusammenhänge zwischen Konstitution und oberflächenaktiven Eigenschaften von Alkylarylsulfonaten. IV (1965)
    New York, NY : Wiley-Blackwell
    Journal für Praktische Chemie/Chemiker-Zeitung 27 (1965), S. 82-90 
    Details
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Die Beziehungen zwischen den physikalisch-chemischen Eigenschaften (Oberflächenpannung, Mizellbildungskonzentration) der wäßrigen Lösungen von (1-7)-Phenyl-n-tetradecan-p-sulfonaten, von (2-7)-Benzyl-n-tridecan-p-sulfonaten und von p-Di-n-alkyl-benzolsulfonaten mit insgesamt 14 C-Atomen in den Seitenketten und der Struktur dieser-Verbindungen werden aufgezeigt und die Resultate mit Literaturangaben verglichen.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/prac.19650270109
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  • 198
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    The 1:2 Hafnium-Sodium Alizarin 3-Sulphonate Chelate (1965)
    New York, NY : Wiley-Blackwell
    Journal für Praktische Chemie/Chemiker-Zeitung 27 (1965), S. 113-116 
    Details
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Formation of a 1:2 hafnium-Alizarin Red S chelate (Λmax520 mμ) has been described. The composition has been arrived at employing absorptiometric measurements using the mole and slope ratio methods. The value of stability constant (log K) as determined by the mole ratio method is 10.2. The system obeys Beer's law from 0.79 ppm. to 35.6 ppm. of hafnium between pH 1.0 and 2.5.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/prac.19650270301
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  • 199
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    Thermolysis of Selenides of Gold, Tin, Iridium, indium, molybdenum, cadmium, bismuth, lead and zinc precipitated by sodium selenide (1965)
    New York, NY : Wiley-Blackwell
    Journal für Praktische Chemie/Chemiker-Zeitung 27 (1965), S. 171-174 
    Details
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermolysis of precipitates formed by gold, tin, iridium, indium, molybdenum, cadmium, bismuth. lead and zinc with the sodium selenide reagent has been studied.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/prac.19650270306
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  • 200
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    Notiz über Ketale von 4-Chlor-4-androsten-3-onen (1965)
    New York, NY : Wiley-Blackwell
    Journal für Praktische Chemie/Chemiker-Zeitung 27 (1965), S. 189-194 
    Details
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Die Bildung der Äthylenketale von 4-Chlor-Δ4-3-ketosteroiden verläuft ohne Verschiebung der Doppelbindung Δ4, wie eine Betrachtung der molaren Rotationsdifferenzen und der Ultraviolett-Spektren zeigt. Es wird die Darstellung von 4-Chlor-17 α-methyltestosteron aus 4-Chlortestosteron beschrieben.
    Additional Material: 3 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/prac.19650270309
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